CN117957342A - Method of making coated glass articles - Google Patents

Method of making coated glass articles Download PDF

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Publication number
CN117957342A
CN117957342A CN202280062866.8A CN202280062866A CN117957342A CN 117957342 A CN117957342 A CN 117957342A CN 202280062866 A CN202280062866 A CN 202280062866A CN 117957342 A CN117957342 A CN 117957342A
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China
Prior art keywords
glass substrate
hafnium
deposition process
vapor deposition
chemical vapor
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CN202280062866.8A
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Chinese (zh)
Inventor
S·瓦拉纳西
M·雷明顿
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Pilkington Group Ltd
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Pilkington Group Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45595—Atmospheric CVD gas inlets with no enclosed reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/25—Metals
    • C03C2217/257—Refractory metals
    • C03C2217/258—Ti, Zr, Hf
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • C03C2218/1525—Deposition methods from the vapour phase by cvd by atmospheric CVD

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The subject matter described herein relates to an atmospheric pressure chemical vapor deposition process for depositing a hafnium-containing coating on a glass substrate by reacting a precursor gas mixture comprising an organohafnium compound, molecular oxygen, and an olefinic hydrocarbon. Also provided are glass articles having a hafnium containing layer formed on the glass substrate.

Description

Method of making coated glass articles
Background
Glass is an article produced when a viscous molten material cools rapidly below its glass transition temperature without sufficient time to form a regular lattice form. Typically, the glass article is formed from a silica-based material, which may comprise about 70-72 wt.% silica (SiO 2). Glass articles are known for use in building and construction products, such as transparent materials for windows, as interior glazing partitions, and as architectural features. In addition to interior and exterior uses, glass articles may also be used as windshields in various types of vehicles. In addition, glass articles can be used as lenses and protective covers for different optical devices, such as for different electronic devices in consumer, scientific and military applications.
Coatings may be deposited on conventional glass articles to enhance properties such as thermal conductivity, electrical resistivity, radiation protection, anti-reflection, and the like. Such coatings are carried out in batch processes under high vacuum conditions and have long processing times.
It is therefore desirable to form hafnium containing coatings at substantially atmospheric pressure and produce them at deposition rates compatible with time critical manufacturing processes (e.g., flat glass production by float process) to produce affordable coatings for optical film stack designs.
Disclosure of Invention
In accordance with and consistent with the present disclosure, an atmospheric pressure CVD process for depositing a hafnium-containing coating on a glass substrate using a precursor gas mixture comprising an organohafnium compound and an olefinic hydrocarbon has surprisingly been discovered.
The subject matter described herein relates to a method of depositing a hafnium-containing coating on a flat glass substrate. More particularly, the subject matter described herein relates to an atmospheric pressure Chemical Vapor Deposition (CVD) process that uses a precursor gas mixture comprising an organohafnium compound and an olefinic hydrocarbon to produce a hafnium-containing coating on a flat glass at a high growth rate.
In one embodiment, a method of forming a coated glass article comprises: providing a glass substrate; and depositing a hafnium-containing coating on the glass substrate using a chemical vapor deposition process, wherein the chemical vapor deposition process utilizes a precursor gas mixture comprising an organohafnium compound, molecular oxygen, and an olefinic hydrocarbon, wherein the precursor gas mixture is introduced into a vapor space above the glass substrate, wherein the organohafnium compound reacts with the olefinic hydrocarbon to produce a hafnium-containing coating on the glass substrate, wherein the hafnium-containing coating exhibits a refractive index of about 1.7 to 1.9.
In another embodiment, a chemical vapor deposition process for depositing a coating on a moving glass substrate comprises: providing a homogeneous precursor gas mixture comprising an organohafnium compound, molecular oxygen, and an olefinic hydrocarbon, each of the organohafnium compound and the olefinic hydrocarbon having a respective thermal decomposition temperature; delivering the precursor gas mixture to a location adjacent to a moving glass substrate to be coated at a temperature below the thermal decomposition temperature of each of the organohafnium compound and the olefinic hydrocarbon, the moving glass substrate having a temperature above the thermal decomposition temperature of the organohafnium compound and being surrounded by an atmosphere having a pressure of about atmospheric pressure; and introducing the precursor gas mixture into a vapor space above the moving glass substrate, wherein the organohafnium compound reacts with the olefinic hydrocarbon to produce a coating on the glass substrate, wherein the coating is a hafnium-containing coating exhibiting a refractive index of about 1.7 to 1.9.
In certain embodiments, the organohafnium compound is a hafnium amino compound (hafnium amido compound).
In certain embodiments, the hafnium amino compound comprises tetrakis (dialkylamino) hafnium Hf (NMe 2)4.
In certain embodiments, the organohafnium compound comprises a tetra (dialkylamino) hafnium compound in the form Hf (NR 1R2)4) where R 1 and R 2 are hydrocarbons having 1,2, or 6 carbon atoms.
In certain embodiments, the hafnium containing coating has a thickness of at least 50 angstroms.
In certain embodiments, the precursor gas mixture further comprises helium.
In certain embodiments, the glass substrate has a temperature of at least 400 ℃, more preferably 425 ℃, when the precursor gas mixture is introduced during the chemical vapor deposition process.
In certain embodiments, the glass substrate has a temperature of 425 ℃ to 700 ℃, more preferably 450 ℃ to 700 ℃, when the precursor gas mixture is introduced during the chemical vapor deposition process.
In certain embodiments, the olefinic hydrocarbon is at least one of ethylene, propylene, and butene. In certain preferred embodiments, the olefinic hydrocarbon is ethylene.
In certain embodiments, the hafnium containing coating is a hafnium oxide coating.
In certain embodiments, the glass substrate comprises soda lime silica glass.
In certain embodiments, the glass substrate is formed by a float glass process.
In certain embodiments, the hafnium containing coating is deposited on the glass substrate at a deposition rate of at least 50 angstroms/second.
In certain embodiments, the coated glass article exhibits a haze of about 0.09% to about 0.54%.
In certain embodiments, the coated glass article exhibits a visible light transmission of about 56% to about 91%.
In certain embodiments, the coated glass article exhibits a film side reflectance of about 8% to about 23%.
In certain embodiments, the method further comprises depositing a silicon dioxide layer between the glass substrate and the hafnium containing coating.
In certain embodiments, the silicon dioxide layer has a thickness of at least 200 angstroms.
In certain embodiments, the method further comprises depositing a tin oxide layer between the glass substrate and the silicon dioxide layer.
In certain embodiments, the temperature of the glass substrate is at least 400 ℃, more preferably 425 ℃, when the precursor gas mixture is introduced into the vapor space above the moving glass substrate.
In certain embodiments, the temperature of the glass substrate is 425 ℃ to 700 ℃, more preferably 450 ℃ to 700 ℃, when the precursor gas mixture is introduced into the vapor space above the moving glass substrate.
In certain embodiments, the chemical vapor deposition process further comprises depositing a silicon dioxide layer between the moving glass substrate and the hafnium containing coating.
In certain embodiments, the chemical vapor deposition process further comprises depositing a tin oxide layer between the moving glass substrate and the silicon dioxide layer.
There is also provided, in accordance with the subject matter of the present invention, a hafnium containing coated glass article. In one embodiment, a hafnium containing coated glass article includes a glass substrate having a surface. The glass article further includes a silicon dioxide layer formed on a surface of the glass substrate and a hafnium-containing layer formed on the silicon dioxide layer.
Detailed Description
It is to be understood that the subject matter described herein may assume various alternative orientations and step sequences, except where expressly specified to the contrary. It is also to be understood that the specific devices and processes described in the following specification are simply exemplary embodiments of the inventive concepts defined in the appended claims. Thus, specific dimensions, directions, flow rates, or other physical characteristics relating to the embodiments disclosed are not to be considered as limiting, unless the claims expressly state otherwise. Furthermore, although the subject matter of the present invention will be described in connection with a float glass process, one of ordinary skill in the art will appreciate that the coating process described herein may be applied to other production processes for depositing hafnium-containing coatings. In the subject matter of the present invention, "hafnium-containing coating" means a hafnium oxide coating, a hafnium nitride coating or a hafnium oxynitride coating.
The processes of the subject matter described herein are typically implemented in connection with the formation of a continuous glass ribbon substrate, such as during float glass manufacturing/production. The subject matter described herein allows for the deposition of hafnium-containing coatings on glass ribbons at high deposition rates, preferably in excess of 50 a/s and more preferably in excess of 75 a/s. It should be appreciated that the deposition rate may be any suitable deposition rate as desired.
When coating a substrate in manufacturing, a high deposition rate is important. This is especially true for float glass manufacturing, where the glass ribbon is traveling at a particular linear velocity and a particular coating thickness is required. To achieve high deposition rates, at least one olefinic hydrocarbon may be used in combination with at least one organohafnium precursor compound to form a hafnium-containing coating without the need for purposeful addition of water vapor, gaseous oxygen, or other oxygen-containing compounds. The deposition rate achieved with preferred embodiments of the subject matter described herein may be greater than or equal to 1.5 times the deposition rate of other known processes for depositing hafnium-containing coatings.
Organohafnium compounds suitable for use in connection with the subject matter described herein are preferably hafnium amino compounds of the general formula Hf (NR 1R2)4, where N is one of ethyl, methyl, propyl, butyl and phenyl, and R 1 and R 2 are the same or different and may be one of an alkyl group having 1-6 carbon atoms or other groups such as phenyl, tolyl, etc. the preferred hafnium amino compound is a tetrakis (dialkylamino) hafnium compound, the particularly preferred precursor material is tetrakis (dimethylamino) hafnium Hf (NMe 2)4).
However, the subject matter described herein is not limited to hafnium amino compounds and other organohafnium compounds may be used to practice the subject matter described herein. For example, bis (methylcyclopentadienyl) hafnium dimethyl Hf [ C 5H4(CH3)]2(CH3)2 ] and bis (methylcyclopentadienyl) methoxy hafnium methyl Hf [ C 5H4(CH3)]2(OCH3)CH3 ] can also be used to form hafnium containing coatings.
It has been found that olefinic hydrocarbons can be used in combination with organohafnium compounds to form hafnium-containing coatings without the need for purposeful addition of water vapor, gaseous oxygen, or other oxygen-containing compounds. The olefinic hydrocarbons which can be used as precursor materials in connection with the subject matter described herein contain one or more double bonds. Preferred olefins for practicing the subject matter described herein include ethylene, propylene, and butylene. A particularly preferred olefinic hydrocarbon is ethylene.
Although it is contemplated that the precursor gases may be combined at or near the surface of the glass substrate, the subject matter described herein relates to the preparation of precursor gas mixtures. The precursor gas mixture comprises an organohafnium compound and an olefinic hydrocarbon. The precursor gas mixture may further preferably comprise a carrier gas or diluent. The carrier gas may comprise one of the gases or a combination of gases. The gas that may comprise the carrier gas includes nitrogen, argon, and/or helium. For example, in one embodiment, the carrier gas comprises helium. In another embodiment, the carrier gas comprises nitrogen and helium. It should be appreciated that any suitable gas or combination of suitable gases may be used as the carrier gas. Regardless of the specific composition, since the precursor gas mixture contains more than one gas, the precursor gases are preferably pre-mixed such that the gas mixture is substantially uniform prior to forming the hafnium-containing coating.
Thermal decomposition of organohafnium compounds and olefinic hydrocarbons can initiate hafnium-containing coating deposition reactions at high rates. Thus, the precursor gas mixture is maintained at a temperature below that at which significant reactions occur before deposition is desired. Preferably, the precursor gas mixture is maintained at a temperature below the thermal decomposition temperature of the organohafnium compound and the olefinic hydrocarbon until deposition is desired.
The precursor gas mixture is delivered to a location adjacent to the moving glass substrate. Prior to deposition, the substrate is at a temperature above the thermal decomposition temperature of the organohafnium compound in the precursor gas mixture. The precursor gas mixture is then introduced into the vapor space above the substrate. The heat from the substrate increases the temperature of the precursor gas mixture above the thermal decomposition temperature of the organohafnium compound. The primary reactants then react with each other to produce a hafnium-containing coating on the substrate.
The deposition rate depends on the particular olefinic hydrocarbon used, the concentration of olefinic hydrocarbon and organohafnium compound, and the temperature of the glass substrate. In particular, the use of ethylene produces a particularly efficient reaction with the tetra (dialkylamino) hafnium compound. The exact role of ethylene in depositing hafnium-containing coatings from organohafnium compounds has not been determined. It should be appreciated that the use of higher concentrations of reactants and high gas flow rates may result in lower overall conversion efficiencies of the reactants to the coating. Thus, the optimal conditions for commercial operation may be different from the conditions that provide the highest deposition rate.
The subject matter described herein allows for the in-line production of hafnium-containing coatings at high rates on moving hot flat glass substrates during the float glass production process. For depositing a hafnium containing coating, the moving glass substrate should be at a temperature of at least 400 ℃ while the precursor gas mixture is introduced into the vapor space above the moving glass substrate. Typically, to practice the subject matter described herein, the glass substrate temperature is about 450 ℃ to 750 ℃. More preferred substrate temperatures are from about 450 ℃ to 700 ℃. Regardless of the temperature of the substrate during deposition, it has been found that hafnium-containing coatings made according to the subject matter described herein have refractive indices of about 1.7 to about 1.9. This allows to achieve the desired optical effect, especially when used in combination with other coatings. It should be noted that the refractive index values described herein are reported as average values over 400-780nm of the electromagnetic spectrum.
When a float glass apparatus is used as an apparatus for practicing the subject matter described herein, the float glass apparatus more particularly includes a pathway portion along which molten glass is conveyed from a melting furnace to a float bath portion where a continuous ribbon of glass is formed by a float process. The glass ribbon advances from the bath portion through an adjacent lehr and cooling portion. The continuous glass ribbon is used as a substrate upon which a hafnium containing coating is deposited according to the subject matter described herein.
The bath portion includes a bottom portion in which the molten tin bath is contained, a top cover, opposing side walls, and end walls. It will be appreciated that the bath may comprise other suitable materials to achieve the desired results. The top cover, side walls and end walls together define an enclosure in which a non-oxidizing atmosphere is maintained to prevent oxidation of the molten tin. Furthermore, the gas distributor beams may be located in the bath section. The gas distributor beams in the bath section may be used to apply a hafnium containing coating to the substrate by the process of the subject matter described herein or to apply an additional coating to the substrate prior to application of the hafnium containing coating. The additional coating may include, for example, tin oxide and/or silicon dioxide.
In operation, molten glass flows in controlled amounts along a path below the conditioning gate (regulating tweel) and down onto the surface of the tin bath. On the tin bath, the molten glass spreads laterally under the influence of gravity and surface tension, as well as some mechanical influence, and it advances through the bath to form a ribbon. The strip is removed on lift rolls and then transported over registration rolls through an annealing furnace and a cooling section. Heaters may be provided within the lehr to gradually reduce the temperature of the glass ribbon as it is conveyed therethrough according to a predetermined schedule. In addition, ambient air may be directed to the glass ribbon, typically by fans in the cooling section.
The application of the hafnium containing coating according to the subject matter of the present invention may be carried out in the float bath section or further along the production line. For example, the hafnium containing coating may be deposited in the gap between the float bath and the lehr or in the lehr itself.
To form the coating in the bath portion, a suitable non-oxidizing atmosphere, typically nitrogen or a mixture of nitrogen and hydrogen with nitrogen being the dominant source, is maintained to prevent oxidation of the molten tin. The atmospheric gas is admitted through a conduit operatively connected to the distribution manifold. The non-oxidizing gas is introduced at a rate sufficient to compensate for normal losses and maintain a slight positive pressure on the order of about 0.001 to about 0.01 atmospheres above ambient atmospheric pressure to prevent permeation of the external atmosphere. For the purposes of the present subject matter, the pressure ranges described above are considered to constitute standard atmospheric pressures. The heat for maintaining the desired temperature conditions in the tin bath and bath housing is provided by radiant heaters within the housing and the glass ribbon itself.
The atmosphere within the lehr is typically atmospheric air. However, when the hafnium-containing coating is formed in the annealing furnace, an inert atmosphere may be maintained in the portion of the annealing furnace where deposition occurs. Similarly, the atmosphere in the gap between the lehr and the bath is typically atmospheric air and bath portion atmosphere, but an inert atmosphere may also be provided when depositing a hafnium containing coating there. In either case, the pressure of the inert atmosphere may be substantially similar to the pressure of the bath portion atmosphere.
The gas distributor beam can be positioned in the bath portion, in the gap between the bath portion and the lehr, or in the lehr to deposit various coatings on the glass ribbon substrate. A gas distributor tube bundle is one form of reactor that may be used to carry out the process of the subject matter described herein.
The construction of a distributor tube bundle suitable for supplying precursor material according to the subject matter of the present invention is an inverted, generally channel-shaped frame formed by spaced apart inner and outer walls and defining two closed chambers. A suitable heat exchange medium is circulated through the closed chamber to maintain the distributor tube bundle at the desired temperature.
The precursor gas mixture is supplied through a supply line. Depending on the location of the deposition, the supply conduit may be surrounded by a cooling fluid. The supply conduit extends along the distributor tube bundle and allows the precursor gas mixture to pass through drop lines spaced along the supply conduit. The supply lines lead to the transfer chambers within headers carried by the frame. The precursor gas mixture entering through the downcomer is discharged through the channel from the transfer chamber to a coating chamber that defines a vapor space open to the glass substrate in which the precursor gas mixture flows along the substrate surface.
Baffles may be provided within the delivery chamber for equalizing the flow of the precursor gas mixture through the distributor tube bundle to ensure that the precursor gas mixture is discharged against the glass substrates in a smooth, laminar, uniform flow completely through the distributor tube bundle. The used precursor gases are collected and removed through an exhaust plenum along the sides of the distributor tube bundle.
Various forms of distributor bundles for chemical vapor deposition are suitable for use in the present process and are known in the art. In one such alternative distributor tube bundle configuration, the precursor gas mixture is introduced through a gas supply conduit in which the precursor gas mixture is cooled by a cooling fluid circulated through a plurality of conduits. The gas supply conduit leads to the gas restrictor through an elongated aperture.
The gas flow restrictor comprises a plurality of metallic strips longitudinally crimped in a sine wave fashion and mounted vertically in abutting relationship with one another, the metallic strips extending along the length of the dispenser. Adjacent curled metal strips are arranged "out of phase" so as to define a plurality of vertical channels therebetween. The vertical channels have a smaller cross-sectional area relative to the cross-sectional area of the gas supply conduit such that the precursor gas mixture is released from the gas restrictor at a substantially constant pressure along the length of the distributor.
The precursor gas mixture is released from the gas restrictor to the inlet side of a substantially U-shaped guide channel, which generally comprises an inlet end tube (inlet leg) and at least one exhaust end tube of a coating chamber open to the glass substrate to be coated, whereby the used precursor gas exits the glass. It should be appreciated that the guide channel may have any suitable size, shape and configuration as desired. The rounded corners of the block defining the coating channel promote uniform laminar flow of the coating parallel to the glass surface across the glass surface to be coated.
Examples
The following examples (where gas volumes are expressed under standard conditions, i.e., one atmosphere and ambient temperature, unless otherwise indicated) are for illustrative purposes only and should not be construed as limiting the subject matter described herein.
The following experimental conditions were applied to comparative examples 1-2 in Table 1, examples 3-4 and examples 5-12 in Table 2.
In examples 1-12, the organohafnium compound used was tetrakis (dimethylamino) hafnium. Preparation and control of organohafnium compound and ethyl acetate EtOAc was achieved by using a multi-source chamber called a bubbler. There is one bubbler for each of the organohafnium compound and EtOAc, and each is maintained at a particular temperature. In examples 1-12, the organohafnium compound bubbler was maintained at a temperature of about 100 ℃. In examples 1-12, the EtOAc bubbler was maintained at a temperature of about 60 ℃. Helium was introduced into the bubbler at the specific flow rates listed in table 1 for delivery of the precursor gas mixture.
At ambient temperature, oxygen and ethylene are gaseous. Thus, neither need to be accommodated and heated in the bubbler. But preferably both are preheated prior to premixing either with the organohafnium compound. The amount of preheating is not critical, but should be sufficient to raise the temperature of either to a temperature similar to that of the organohafnium compound.
The glass substrate is heated to the desired temperature and transported through a laboratory furnace. The laboratory oven had a 25.4cm wide bi-directional coater located over the glass substrate. The coater is adapted to dispense gaseous reactants onto the surface of the glass substrate to form a coating or layer stack by chemical vapor deposition.
Table 1 summarizes deposition flow rates of precursor gas mixtures delivered to the surface of a glass substrate according to the subject matter described herein. The various reactants described below are premixed into a uniform precursor gas mixture prior to introduction into the vapor space above the glass substrate. When the precursor gas mixture was introduced into the vapor space above the glass substrate, the substrate used in example 1 was at a temperature of 454 ℃, the substrate used in example 2 was at a temperature of 632 ℃, the substrate used in example 3 was at a temperature of 632 ℃, and the substrate used in example 4 was at a temperature of 632 ℃.
Examples 1-3 were performed under static conditions using a soda lime silica glass substrate on which a 200 angstrom thick layer of silicon dioxide had been previously deposited. Example 4 was performed under dynamic conditions at a line speed of 75 inches/min using a soda lime silica glass substrate on which a 200 angstrom thick layer of silicon dioxide had been previously deposited.
Table 1: glass substrate/silica/hafnium coating
Comparative example Carrier gas 1 Carrier gas 2 Hf(NMe2)4 EtOAc O2 C2H4
1 15 He 15He 3 1 0 0
2 15He 15He 5 0 3 0
Examples
3 15He 15He 5 0 3 5
4 15He 15He 5 0 3 5
Note that: all flow rates are in standard liters per minute.
In comparative examples 1 and 2, a hafnium-containing layer was not formed. In example 3, the hafnium-containing layer was formed at a rate of 160 a/s. In example 4, the hafnium-containing layer was formed at a rate of about 85 a/s. The hafnium containing coating thickness was optically measured.
Table 2 summarizes the input parameters and coating properties for examples 5-12 according to the subject matter described herein. The various reactants described below are premixed into a uniform precursor gas mixture prior to introduction into the vapor space above the glass substrate. Examples 5-12 were conducted under static conditions using a glass substrate. In addition to the input parameters shown in Table 2 for examples 5-12, molecular oxygen (O 2) was also introduced. The source of molecular oxygen for examples 5-12 is the ambient atmosphere.
Table 2: glass substrate/silica/hafnium coating
The thickness of the coating of example 9 deposited at lower substrate temperatures is not sufficient to be acceptable for most applications.
It should be noted that the process of the subject matter described herein may be repeated as desired on a given substrate to form a coating consisting of several successive layers, each of which is not necessarily identical in composition. Of course, it is apparent that for a given reactant flow rate; the thickness of the coating depends on the rate of movement of the substrate. Under these conditions, the reaction station can be increased if necessary by juxtaposing two or more coating devices. In this way, successive layers are superimposed before the layer has time to cool, resulting in a particularly uniform overall coating and/or coating stack.
In practicing the subject matter described in this disclosure, it may be preferable to apply a layer of material that acts as a sodium diffusion barrier between the glass substrate and the hafnium-containing coating. For example, it has been found that coated glass articles exhibit lower haze when hafnium containing coatings deposited according to the subject matter described herein are applied to glass substrates with a sodium diffusion layer therebetween, as opposed to directly on the glass. This may be especially true when the glass substrate is soda lime silica glass. Thus, in one embodiment, a sodium diffusion layer comprising silicon dioxide is formed over the surface of the glass substrate. In this embodiment, the silicon dioxide layer, preferably formed using conventional CVD techniques, is preferably at least 200 angstroms thick.
In another embodiment, a tin oxide layer is first deposited over the surface of the glass substrate, and a silicon dioxide layer is deposited thereon. A tin oxide layer is deposited and adheres to the surface of the glass substrate. This results in a tin oxide/silicon dioxide substructure formed intermediate the glass and the subsequently deposited layers of the hafnium containing coating. In this embodiment, the silica film not only serves as a sodium diffusion barrier, but in combination with the first (undoped) tin oxide film helps to suppress iridescence in the resulting coated glass article. The use of such anti-iridescence layers is disclosed in U.S. patent No. 4,377,613, which is incorporated herein by reference in its entirety.
The subject matter of the present invention has been disclosed in what is considered to be the preferred embodiments thereof. It must be understood that this particular embodiment has been set forth only for purposes of illustration and that the subject matter described herein may be practiced otherwise than as specifically illustrated without departing from its spirit or scope.

Claims (18)

1. A method of forming a coated glass article comprising:
Providing a glass substrate; and
A hafnium-containing coating is deposited on the glass substrate using a chemical vapor deposition process,
Wherein the chemical vapor deposition process utilizes a precursor gas mixture comprising an organohafnium compound, molecular oxygen, and an olefinic hydrocarbon,
Wherein the precursor gas mixture is introduced into a vapor space above the glass substrate,
Wherein the organohafnium compound and the olefinic hydrocarbon react to produce the hafnium-containing coating on the glass substrate,
Wherein the hafnium containing coating exhibits a refractive index of about 1.7 to 1.9.
2. A chemical vapor deposition process for depositing a coating on a moving glass substrate to form a coated glass article, comprising:
Providing a homogeneous precursor gas mixture comprising an organohafnium compound, molecular oxygen, and an olefinic hydrocarbon, each of the organohafnium compound and the olefinic hydrocarbon having a respective thermal decomposition temperature;
Delivering the precursor gas mixture to a location adjacent to a moving glass substrate to be coated at a temperature below the respective thermal decomposition temperatures of the organohafnium compound and the olefinic hydrocarbon, the moving glass substrate having a temperature above the thermal decomposition temperature of the organohafnium compound and being surrounded by an atmosphere having a pressure of about atmospheric pressure; and is combined with
Introducing the precursor gas mixture into a vapor space above a moving glass substrate, wherein an organohafnium compound reacts with an olefinic hydrocarbon to produce a coating on the glass substrate, wherein the coating is a hafnium-containing coating exhibiting a refractive index of about 1.7 to 1.9.
3. The method according to claim 1 or the chemical vapor deposition process according to claim 2, wherein the organohafnium compound is a hafnium amino compound.
4. A method or chemical vapor deposition process according to claim 3, wherein the hafnium amino compound comprises tetrakis (dialkylamino) hafnium Hf (NMe 2)4.
5. The method according to any one of claims 1, 3 and 4, or the chemical vapor deposition process according to any one of claims 2 to 4, wherein the organohafnium compound comprises a tetra (dialkylamino) hafnium compound in the form of Hf (NR 1R2)4), wherein R 1 and R 2 are hydrocarbons having 1, 2 or 6 carbon atoms.
6. The method according to any one of claims 1 and 3 to 5, or the chemical vapor deposition process according to any one of claims 2 to 5, wherein the hafnium containing coating has a thickness of at least 50 angstroms.
7. The method according to any one of claims 1 and 3 to 6, or the chemical vapor deposition process according to any one of claims 2 to 6, wherein the precursor gas mixture further comprises helium.
8. A method according to any one of claims 1 and 3 to 7, or a chemical vapour deposition process according to any one of claims 2 to 7, wherein the temperature of the glass substrate is at least 400 ℃, preferably 425 ℃, when the precursor gas mixture is introduced into the vapour space.
9. A method according to any one of claims 1 and 3 to 8, or a chemical vapour deposition process according to any one of claims 2 to 8, wherein the temperature of the glass substrate is between 425 ℃ and 700 ℃, preferably between 450 ℃ and 700 ℃, when the precursor gas mixture is introduced into the vapour space.
10. The method according to any one of claims 1 and 3 to 9, or the chemical vapor deposition method according to any one of claims 2 to 9, wherein the olefinic hydrocarbon is at least one of ethylene, propylene and butene.
11. The method according to any one of claims 1 and 3 to 10, or the chemical vapor deposition method according to any one of claims 2 to 10, wherein the olefinic hydrocarbon is ethylene.
12. The method according to any one of claims 1 and 3 to 11, or the chemical vapor deposition process according to any one of claims 2 to 11, wherein the hafnium containing coating is a hafnium oxide coating.
13. A method according to any one of claims 1 and 3 to 12, or a chemical vapour deposition process according to any one of claims 2 to 12, wherein the glass substrate or the moving glass substrate comprises soda-lime-silica glass.
14. A method according to any one of claims 1 and 3 to 13, or a chemical vapour deposition process according to any one of claims 2 to 13, wherein the glass substrate or the moving glass substrate is formed by a float glass process.
15. The method according to any one of claims 1 and 3 to 14, or the chemical vapor deposition process according to any one of claims 2 to 14, wherein the hafnium containing coating is deposited on the glass substrate or the moving glass substrate at a deposition rate of at least 50 angstroms/sec.
16. The method according to any one of claims 1 and 3 to 15, or the chemical vapor deposition process according to any one of claims 2 to 15, further comprising depositing a silicon dioxide layer between the glass substrate or the moving glass substrate and the hafnium containing coating.
17. The method or chemical vapor deposition process according to claim 16, wherein the silicon dioxide layer has a thickness of at least 200 angstroms.
18. The method or chemical vapor deposition process according to claim 16 or 17, further comprising depositing a tin oxide layer between the glass substrate or the moving glass substrate and the silicon dioxide layer.
CN202280062866.8A 2021-08-26 2022-08-25 Method of making coated glass articles Pending CN117957342A (en)

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US4377613A (en) 1981-09-14 1983-03-22 Gordon Roy G Non-iridescent glass structures
CA2159296C (en) * 1994-10-14 2007-01-30 Michel J. Soubeyrand Glass coating method and glass coated thereby
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